CN114990350B - Method for deeply removing TOC and residual organic matters in zinc sulfate solution - Google Patents
Method for deeply removing TOC and residual organic matters in zinc sulfate solution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 63
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 31
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 31
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 31
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 116
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 238000005273 aeration Methods 0.000 claims abstract description 14
- 239000006228 supernatant Substances 0.000 claims description 130
- 239000000243 solution Substances 0.000 claims description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 230000003472 neutralizing effect Effects 0.000 claims description 38
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000009854 hydrometallurgy Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000011403 purification operation Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000010414 supernatant solution Substances 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 144
- 230000035484 reaction time Effects 0.000 description 38
- 238000007792 addition Methods 0.000 description 36
- 229920005610 lignin Polymers 0.000 description 26
- 238000002474 experimental method Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 8
- 239000005750 Copper hydroxide Substances 0.000 description 8
- 229910001956 copper hydroxide Inorganic materials 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002562 thickening agent Substances 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920005551 calcium lignosulfonate Polymers 0.000 description 5
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- -1 calcium lignan Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 229930013686 lignan Natural products 0.000 description 1
- 235000009408 lignans Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QKGIPGSKJBOHSL-UHFFFAOYSA-N naphthalen-2-amine;hydrochloride Chemical compound [Cl-].C1=CC=CC2=CC([NH3+])=CC=C21 QKGIPGSKJBOHSL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000004801 process automation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for deeply removing TOC and residual organic matters in zinc sulfate solution, which comprises the following steps of; adopts an ozone aeration method and a strong oxidation method. The invention adopts an alkaline strong oxidation method to deeply remove the residual lignosulfonate and the decomposition products thereof in the solution, and adopts an ozone aeration method to remove the TOC in the second neutralization solution.
Description
Technical Field
The invention belongs to the technical field of zinc metallurgy, and particularly relates to a method for deeply removing TOC and residual organic matters in zinc sulfate solution.
Background
With the regulations of energy-saving and emission-reduction related industries, for example, "newly built lead-zinc smelting: the direct current power consumption of zinc precipitation in the production of electric zinc is reduced to below 2900 kilowatt-hour/ton, the electrolysis current efficiency is more than 88%, and the existing smelting enterprises need to save energy and reduce consumption by technical transformation so as to reach the energy consumption level of new enterprises. The current zinc smelting electric zinc direct current power consumption in the prior art is about 3300-3500Kw.h/t, the electrolysis efficiency is 80-85% (but the cell voltage is 380-385V higher), and a great improvement space is still provided; in addition, the TOC of the solution is up to 150mg/L, and in the electrolytic production process, the phenomenon of plate burning and dissolution of the organic matters often occurs, so that the zinc electrolysis energy consumption is increased suddenly, the energy consumption is 900-1200cet/t, the standard entry condition is not reached yet, and the energy consumption needs to be further reduced so as to meet the current energy saving and consumption reduction requirements. Therefore, the research of carrying out solution deep purification, reducing direct current unit consumption and removing TOC and residual organic matters in the solution is particularly urgent around long-period electrolysis.
Therefore, it is a urgent need for those skilled in the art to provide a method for deeply removing TOC and residual organics from zinc sulfate solution.
Disclosure of Invention
In view of this, the invention provides a method for deeply removing TOC and residual organic matters in zinc sulfate solution, which adopts alkaline strong oxidation method to deeply remove residual lignosulfonate and its decomposition products, and ozone aeration method to remove TOC in second neutralization solution.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for deeply removing TOC and residual organic matters in zinc sulfate solution adopts an ozone aeration method and a strong oxidation method.
In the zinc hydrometallurgy neutralization iron removal section, hydrogen peroxide is sprayed into an iron removal reaction first tank through pressurized oxygen-enriched air, so that the oxidation efficiency of oxygen to ferrous ions in a zinc sulfate solution is improved, the formation of goethite is promoted, and simultaneously, lignin decomposition products (reducing sugar) in the solution are oxidized into inorganic carbon by combining the hydrogen peroxide with the oxygen, so that the purpose of removing the lignin decomposition products in the solution is achieved; simultaneously, ozone is introduced into an iron removal reaction tail tank, hydrogen peroxide which is incompletely reacted in the solution is combined to decompose TOC in the solution, then a flocculating agent is added into an outlet of the reaction tank, the solution enters a thickener for sedimentation solid-liquid separation, TOC decomposition products in the solution are adsorbed into slag in the goethite sedimentation process, and the purpose of TOC removal is achieved
Preferably, the oxidant used in the strong oxidation process is H 2O2.
The standard oxidation-reduction potential of O 3、H2O2 is 2.07V and 1.77V respectively, and the common point of the two is that other impurities are not carried in the oxidation process, the product after the decomposition of the former is O 2, the product after the decomposition of the latter is H 2O、O2, so that the oxidation-reduction catalyst is a green and environment-friendly strong oxidation reagent, not only can remove scattered elements, but also can remove organic matters.
It is known that strong oxidizing agents such as potassium permanganate and sodium persulfate can remove organic matters, but the problems of high unit consumption, high purchase price and the like exist.
H 2O2 has stronger oxidizing capability per se, and an H 2O2-O3 oxidizing system is used in combination, so that the oxidizing and degrading effects on organisms can be generated by generating hydroxyl free radicals besides self oxidizing effects, and the oxidizing efficiency is greatly improved. The production is carried out by neutralizing each section of solution, carrying out H 2O2-O3 combined action treatment, oxidizing and decomposing organic matters in the solution to generate CO 2 and the like, removing Se, te and other scattered metals, oxidizing and removing high-valence metals
Preferably, the strong oxidation process and the ozone aeration process are performed in a reaction tank of pre-neutralised supernatant and/or a neutralised supernatant.
Preferably, the strong oxidation process is carried out in a reaction head tank.
Preferably, the ozone aeration method is performed in a reaction tail tank.
Preferably, barium carbonate is added into the zinc sulfate solution.
Preferably, the adding point of the barium sulfate is any one of a supernatant, a neutralization supernatant and a new liquid.
Preferably, the method further comprises adding activated carbon to the pre-neutralization supernatant and/or a neutralization supernatant.
Preferably, the method further comprises the step of activating the secondary neutralization supernatant by radio frequency.
Preferably, the H 2O2 is injected into the zinc sulfate solution by pressurized oxygen-enriched air.
Compared with the prior art, the invention has the following beneficial effects:
(1) The lignosulfonate and the decomposition products thereof in the zinc hydrometallurgy flow have high removal efficiency, other impurities harmful to the process are not carried in the purification process, the quality of zinc sulfate solution can be improved, the solution quality is stable, the process automation degree is high, and the production cost is low.
(2) According to the invention, ozone aeration is adopted to remove TOC in the solution, new auxiliary materials are not required to be added in the process, other new impurities in the process are not introduced, and meanwhile, the aeration pipe is installed by utilizing the second-site neutralization supernatant storage tank without separately constructing a concentration tank, so that the input cost can be greatly saved.
(3) The hydrogen peroxide is sprayed into the zinc sulfate solution through the pressurized oxygen-enriched air, so that the rapid and uniform mixing can be realized, the free radicals of the hydrogen peroxide are promoted to efficiently decompose zinc, the residual lignosulfonate and the decomposition products thereof in the zinc sulfate solution are leached out through the pressurized leaching, and the purpose of deeply removing the organic matters is achieved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of TOC removal rate for various reaction times for a test set of the present invention;
FIG. 2 is a graph of TOC removal rates for different addition flows for a test set of the present invention;
FIG. 3 is a graph showing TOC removal rates at various reaction times for a test set of the present invention;
FIG. 4 is a graph showing TOC removal rates for various additions in the test group of the present invention;
FIG. 5 is a graph of lignin removal at various reaction times for a test panel of the present invention;
FIG. 6 is a graph showing lignin removal for different barium carbonate additions in the test set of the present invention;
FIG. 7 is a graph of a first set of removal rates for a test set of RF experiments according to the present invention;
FIG. 8 is a graph of TOC removal rate for various reaction times for a test set of the present invention;
FIG. 9 is a third set of removal rate curves for the inventive test set of RF experiments;
FIG. 10 is a process flow diagram of an embodiment of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to FIG. 10, a method for deeply removing TOC and residual organic matters in zinc sulfate solution specifically comprises the following steps:
Performing a strong oxidation method and an ozone aeration method in a reaction tank for pre-neutralizing supernatant and a neutralizing supernatant, wherein an oxidant adopted in the strong oxidation method is H 2O2,H2O2 which is sprayed into zinc sulfate solution by pressurized oxygen-enriched air; the strong oxidation method is carried out in a reaction first tank, and the ozone aeration method is carried out in a reaction tail tank.
Test examples
The solution used in the experiment is a direct leaching solution of zinc concentrate by oxygen enrichment and pressurization of the group-specific process technology (Hulun Bei Erchi macro mineral Co., ltd.), and the solution mainly used in the experiment is: copper precipitation post-liquid, pre-neutralization supernatant, first neutralization supernatant, second neutralization supernatant, middle supernatant solution and first-stage purified post-liquid; wherein the double solution composition is shown in table 1 below;
TABLE 1 Zinc System solution composition Table
An ozone generator: ozone concentration of 0-300 mg/L and flow rate of 0-5L/min (QLO-10G) is generated;
radio frequency activation system: the solution in the reaction cavity is subjected to radio frequency activation treatment by using radio frequency activation equipment through microwave activation, so that the utilization rate of ozone and hydrogen peroxide in the reaction process is improved; the working frequency is any point in the frequency band of 900-930 MHz; (BS-HB 800C);
The hydrogen peroxide is 30% analytically pure hydrogen peroxide;
The barium carbonate is industrial grade barium carbonate, and the content is 90%;
The calcium aluminate is calcium aluminate for water treatment;
The active carbon is Chongqing Hua Xi-320 mesh active carbon;
the sulfuric acid is 98% of analytically pure concentrated sulfuric acid, which is prepared into 1:1 dilute sulfuric acid is used, and is mainly used for neutralizing the supernatant to regulate acid;
ferrous sulfate heptahydrate is of industrial grade and has the content of 90 percent and is used for adjusting the content of Fe 2+ in the second neutralization supernatant; correlation measurement method
(1) Method for measuring total organic carbon in solution in zinc hydrometallurgy process
Toc=tc-IC (TC: total carbon; TOC: total organic carbon; IC: inorganic carbon);
preparing TC solution: the potassium hydrogen phthalate 0.2125g is weighed and dissolved in water to be constant volume to a volumetric flask of 100ml to obtain the TC concentration of 1000mg/L. Transfer 2ml to a 100ml volumetric flask to give a TC concentration of 20mg/L.
IC solution preparation: the IC concentration is 1000mg/L by weighing 0.3497g of sodium bicarbonate and 0.4412g of sodium carbonate to a volume of 100ml of volumetric flask. Transfer 2ml to a 100ml volumetric flask to obtain IC concentration 20mg/L.
1-10 Ml of the solution is taken according to the concentration of the sample, placed in a 100ml colorimetric tube, added with sulfuric acid at pH=4.0, and analyzed and measured by using an organic carbon analyzer. The sample is automatically injected into a sample reaction chamber for catalytic combustion, water is evaporated, carbon is oxidized into carbon dioxide, the intensity value is detected by a specific detector and is converted into a concentration value, and the TOC content of the sample is obtained.
(2) Method for measuring reducing sugar
Taking 5-10 mL of a sample, adding 70mL of sulfuric acid solution, accurately adding 3.0mL of potassium permanganate standard solution, boiling the sample for 5-10 min, taking down the sample, adding 3.0mL of sodium oxalate standard solution equivalent to potassium permanganate while the sample is hot, and immediately dripping potassium permanganate solution (4.10) to the reddish color as an end point when the solution is free from black particles and clear after shaking.
(3) Method for measuring lignin in production process liquid
Sucking 5mL of the sample in a 250mL beaker, blowing water, adjusting the pH to be=3 by using a hydrochloric acid solution, adding 5mL of beta-naphthylamine hydrochloric acid solution while stirring, covering a surface dish, digesting for 1h in a boiling water bath, forming yellow fine particle precipitate after heating the solution, turning into dark brown precipitate, and taking down. Filtering with constant weight (baking at 50deg.C for 1 h) and weighing filter paper, washing the precipitate with hot hydrochloric acid solution for 3 times, washing the precipitate with hot water for about 9 times, and baking the filter paper with the precipitate to constant weight (baking at 50deg.C for 1 h), wherein the increased weight is the precipitate weight;
Research on TOC removal by mixing ozone and hydrogen peroxide
(1) Study of TOC removal by ozone aeration: a small amount of Fe 2+ and lower acidity are needed to exist in the TOC in the ozone removal solution, fe 2+ is oxidized into Fe 3+ and then hydrolyzed to form Fe (OH) 3 colloid and FeOOH precipitate to take away TOC in the solution, so that the TOC in the solution is removed;
① Selection of optimal addition point for removing TOC by ozone
A. Target addition point: copper deposition operation, pre-neutralization operation, first neutralization operation, second neutralization operation and first-stage purification operation;
b. experimental conditions: the temperature is 80-85 ℃, the time is 70min, the ozone concentration is 300mg/L, and the flow is 2.5L/min;
experimental results: see table 2:
TABLE 2 results of ozone removal TOC addition Point experiments
From the data in table 2, it can be seen that:
TOC removal efficiency: the first neutralization operation is a pre-neutralization operation, the second neutralization operation is a copper precipitation operation, and the first purification operation is a copper precipitation operation; thus, the pre-neutralization supernatant, the first neutralization supernatant, the second neutralization supernatant are selected in combination with the tapping angle.
② Optimum reaction time for removing TOC by ozone
A. solution selection: pre-neutralization supernatant, primary neutralization supernatant, secondary neutralization supernatant;
b. Experimental conditions: the temperature is 80-85 ℃, the time is 60min, 70min, 80min, 90min, 100min and 110min, the ozone concentration is 300mg/L, and the flow is 2.5L/min;
c. the experimental results are shown in Table 3 and FIG. 1.
TABLE 3 results of TOC removal reaction time experiments
As can be seen from the data in table 3 and fig. 1:
1) Pre-neutralization supernatant: the TOC removal rate is increased and then reduced along with the reaction time, and the curve reaches a peak value 31.41% when the reaction time is 100 min;
2) Neutralizing the supernatant: the TOC removal rate is increased and then reduced along with the overall trend of the reaction time, and the curve reaches the peak value of 23.59% when the reaction time is 90min;
3) Second, neutralizing supernatant: the TOC removal rate increases and decreases with the overall trend of the reaction time, and the curve reaches the peak value of 20.82% when the reaction time is 70 min.
③ Optimum adding flow rate for removing TOC by ozone
A. solution selection: pre-neutralization supernatant, primary neutralization supernatant, secondary neutralization supernatant.
B. Experimental conditions: the temperature is 80-85 ℃; time: pre-neutralizing supernatant for 100min, first neutralizing supernatant for 90min, second neutralizing supernatant for 70min; ozone: the concentration is 300mg/L, and the flow pair is 1.5L/min, 2.5L/min, 3.5L/min, 4.5L/min, 5.5L/min and 6.0L/min;
c. the experimental results are shown in table 4 and fig. 2;
table 4 ozone removal TOC addition flow experiment results
As can be seen from table 4 and fig. 2:
1) Pre-neutralization supernatant: the TOC removal rate is firstly increased and then decreased along with the ozone adding flow, and the curve reaches a peak value 35.52% when the ozone adding flow is 3.5L/min (the ozone concentration is 300mg/L, the ozone adding flow is 3.5L/min, the reaction time is 100min, and the solution volume is 2L, and the optimal adding amount is 6.3 kg/h);
2) Neutralizing the supernatant: the TOC removal rate is firstly increased and then decreased along with the ozone adding flow, and the curve reaches the peak value of 29.31% when the ozone adding flow is 4.5L/min (the ozone concentration is 300mg/L, the ozone adding flow is 4.5L/min, the reaction time is 90min, and the solution volume is 2L, and the optimal adding amount is 8.1 kg/h);
3) Second, neutralizing supernatant: the TOC removal rate is increased and then decreased along with the ozone adding flow, and the curve reaches 28.64% of the peak value when the ozone adding flow is 3.5L/min (the ozone concentration is 300mg/L, the ozone adding flow is 3.5L/min, the reaction time is 70min, and the solution volume is 2L, and the optimal adding amount is 6.3 kg/h).
④ Knot (S)
A. the most reasonable ozone addition point: a pre-neutralization operation, a first neutralization operation and a second neutralization operation belong to an operation groove;
b. optimal reaction time: pre-neutralization operation for 100min, first neutralization operation for 90min, and second neutralization operation for 70min;
c. The optimal addition amount is as follows: the pre-neutralization operation is 6.3kg/h, the first neutralization operation is 8.1kg/h, and the second neutralization operation is 6.3kg/h;
By using the process conditions for removing TOC by ozone, the TOC removal rate of ozone in zinc sulfate solution can reach more than 30%.
(2) Technical research on TOC removal by hydrogen peroxide strong oxidation: the strong oxidizing property of hydrogen peroxide is utilized to be matched with ozone, fe 2+ in the solution is oxidized into Fe 3+, and the TOC in the zinc sulfate solution is removed through the hydrolysis of Fe 3+;
① Selection of optimal adding point for removing TOC (total organic carbon) from hydrogen peroxide
A. target addition point: copper deposition operation, pre-neutralization operation, first neutralization operation, second neutralization operation and first purification operation.
B. Experimental conditions: the temperature is 80-85 ℃ and the time is 70min, and the addition amount of hydrogen peroxide is as follows: 4.5g/L;
c. The experimental results are shown in Table 5.
TABLE 5 Experimental results for TOC removal by Hydrogen peroxide
From the data in table 5, it can be seen that:
TOC removal efficiency: the first neutralization operation is a pre-neutralization operation, a copper deposition operation, a second neutralization operation and a first-stage purification operation;
therefore, the pre-neutralization supernatant and the neutralization supernatant are selected as hydrogen peroxide adding points according to experimental results;
② Optimum reaction time for removing TOC from hydrogen peroxide
A. solution selection: pre-neutralizing supernatant, a neutralizing supernatant;
b. Experimental conditions: the temperature is 80-85 ℃, the time is 50min, 60min, 70min, 80min, 90min, 100min, 110min and 120min, and the hydrogen peroxide adding amount is 4.5g/L;
c. the experimental results are shown in table 6 and fig. 3:
TABLE 6 Experimental results of TOC removal reaction time for Hydrogen peroxide
As can be seen from table 6 and fig. 3:
1) Pre-neutralization supernatant: the TOC removal rate is increased and then reduced along with the reaction time, and the curve reaches the peak value of 36.23% when the reaction time is 60 min;
2) Neutralizing the supernatant: the TOC removal rate is increased and then reduced along with the reaction time, and the curve reaches a peak value 34.38% when the reaction time is 70 min;
③ Optimum adding amount for removing TOC of hydrogen peroxide
A. solution selection: pre-neutralizing supernatant, a neutralizing supernatant;
b. Experimental conditions: the temperature is 80-85 ℃, the reaction time is 60min for pre-neutralizing the supernatant, 70min for neutralizing the supernatant, and the addition amount of hydrogen peroxide is 0.5g/L, 1.5g/L, 2.5g/L, 3.5g/L, 4.5g/L and 5.5g/L;
c. the experimental results are shown in Table 7 and FIG. 4.
TABLE 7 Experimental results of TOC removal by Hydrogen peroxide
As can be seen from table 7 and fig. 4:
1) Pre-neutralization supernatant: the TOC removal rate is increased and then decreased with the addition amount, and the curve reaches a peak value 37.27% when the addition amount is 3.5 g/L;
2) Neutralizing the supernatant: the TOC removal rate is increased and then decreased with the addition amount, and the curve reaches 35.20% of the peak value when the addition amount is 4.5 g/L;
④ Knot (S)
A. in combination with the production site, the most reasonable adding point of hydrogen peroxide is as follows: a first neutralizing operation tank (pre-neutralizing supernatant), a second neutralizing operation tank # 1 and # 2 (first neutralizing supernatant);
b. optimal reaction time: a first neutralization operation groove for 60min and a second neutralization operation groove for 70min;
c. the optimal addition amount is as follows: a first neutralization operation groove 3.5g/L and a second neutralization operation groove 4.5g/L;
By using the technological condition for removing TOC by hydrogen peroxide, the TOC removal rate of hydrogen peroxide in zinc sulfate solution can reach more than 30%.
(3) Research on TOC removal by mixing ozone and hydrogen peroxide: in order to verify whether the mutual influence exists in the simultaneous use of the ozone and the hydrogen peroxide, the ozone and the hydrogen peroxide are added together under the respective optimal conditions of the pre-neutralization supernatant fluid and the neutralization supernatant fluid, and whether the mutual influence exists between the pre-neutralization supernatant fluid and the neutralization supernatant fluid is verified;
① Mixing impurity removal experiment of ozone and hydrogen peroxide in pre-neutralization supernatant
A. solution selection: pre-neutralizing the supernatant;
b. Experimental conditions: the temperature is 80-85 ℃ and the time is as follows: ozone is 100min, hydrogen peroxide is 60min (hydrogen peroxide is added after ozone is introduced for 40 min), the ozone concentration is 300mg/L, the adding flow is 3.5L/min, and the adding amount of hydrogen peroxide is 4.5g/L;
c. The experimental results are shown in table 8:
TABLE 8 mixing and impurity removal test results of ozone and Hydrogen peroxide in Pre-neutralized supernatant
From the data in Table 8, it can be seen that: the mixed use of ozone and hydrogen peroxide in the pre-neutralization supernatant greatly improves TOC removal efficiency, and can reach 40%, which proves that the use effect of ozone and hydrogen peroxide in the pre-neutralization supernatant is better.
The principle of adding points of ozone and hydrogen peroxide is as follows: the experimental research results show that the optimal adding points of the ozone in the system are pre-neutralization supernatant, first neutralization supernatant and second neutralization supernatant, and the optimal adding points of the hydrogen peroxide are pre-neutralization supernatant and first neutralization supernatant; the process flow is that the precursor liquid enters a pre-neutralization thickener after passing through 2 operation tanks for pre-neutralization, the supernatant fluid of the pre-neutralization thickener enters a neutralization thickener for 3 operation tanks, then enters a neutralization thickener, the supernatant fluid of the neutralization thickener enters a second neutralization tank for 4 operation tanks, and finally enters a second neutralization thickener to obtain the supernatant fluid of the second neutralization thickener;
The solution properties of the pre-neutralization tail tank and the first neutralization tank are similar to those of the pre-neutralization supernatant, the solution properties of the first neutralization tail tank and the second neutralization tank are similar to those of the first neutralization supernatant, and the solution properties of the second neutralization tail tank are similar to those of the second neutralization tank. So according to the difference of the optimal reaction time of the ozone and the hydrogen peroxide at the optimal adding point, when the optimal adding point is the pre-neutralization supernatant, the ozone adding point is a pre-neutralization tail tank, and the hydrogen peroxide adding point is a neutralization head tank; when the optimal adding point is a neutralization supernatant, the ozone adding point is a neutralization tail tank, and the hydrogen peroxide adding point is a second neutralization head tank; when the optimal adding point is the second neutralizing supernatant liquid, the ozone adding point is the second neutralizing tail tank, and the adding point is added with the previous operation tank as the second neutralizing 3# tank in order to ensure that the ozone can reach sufficient reaction time.
② Mixing and impurity removing experiment of ozone and hydrogen peroxide in neutralization supernatant
A. solution selection: a neutralization supernatant;
b. Experimental conditions: the temperature is 80-85 ℃ and the time is as follows: ozone for 90min, hydrogen peroxide for 70min (hydrogen peroxide is added after ozone is introduced for 20 min), the ozone concentration is 300mg/L, the adding flow is 4.5L/min, and the adding amount of the hydrogen peroxide is 4.5g/L;
c. The experimental results are shown in Table 9;
TABLE 9 mixing and impurity removal test results of ozone and Hydrogen peroxide in neutralization supernatant
From the data in Table 9, it can be seen that: the mixed use of ozone and hydrogen peroxide in the first neutralization supernatant has a great improvement on TOC removal efficiency, and can reach more than 40%, which proves that the use effect of the ozone and the hydrogen peroxide in the first neutralization supernatant is better.
③ Knot (S)
Experiments prove that the TOC removal rate of the zinc sulfate solution is improved to more than 40% by adding ozone and hydrogen peroxide together, and a theoretical basis is provided for the industrial application of ozone and hydrogen peroxide.
Study of lignosulfonate removal technique
① Removal using acidic environments
Wherein, the relation between the solubility of the calcium lignosulfonate and the pH is shown in Table 9,
TABLE 10 solubility of calcium Lignosulfonate versus pH
| PH (solvent) | Mass/(g. L -1) of dissolved calcium lignan |
| 1～2 | 15.3400 |
| 5～6 | 17.3760 |
| 7 | 23.4800 |
| 9～10 | 75.1600 |
| 13～14 | 89.9800 |
As can be seen from table 10:
1) The calcium lignosulfonate has good water solubility;
2) The solubility of calcium lignosulfonate in alkaline solutions is greater than in acidic solutions, and increases significantly with increasing pH.
In combination with the actual production situation, the oxygen pressure leaching primary supernatant belongs to acidity (pH=1, nearby), so that the primary supernatant is often controlled to be nearby pH=1 or slightly less than 1 according to the process requirement of neutralization and iron removal in the actual production process, and the direct entry of lignin sulfonate into zinc sulfate solution is facilitated; the oxygen pressure leaching secondary starting acid is generally 150g/L, and the final acid is generally 20-30 g/L, which is beneficial to reducing the dissolution amount of calcium lignosulfonate (including the residual in new input or waste electrolyte);
② Barium carbonate removal
The method [5] for measuring the content of the acid-insoluble lignin by coprecipitation of the acid-insoluble lignin and barium sulfate (barium chloride reacts with sulfuric acid) is used as a reference in the paper industry.
Barium chloride cannot be used for the zinc system, and corrosion is aggravated by introducing chloride ions to initiate anode plates and wet environmental equipment.
Then, according to the method, experimental study is carried out, and lignin and barium sulfate in the sulfuric acid solution are co-precipitated by using lignin-barium sulfate precipitation generated after adding barium carbonate under an acidic condition, so that the purpose of removing lignin is achieved.
③ Selection of the best point of addition of barium carbonate
The lignin content of each section of zinc sulfate solution in the zinc system is analyzed and measured, so that the zinc sulfate solution with the highest lignin content in the zinc system is obtained as a section of supernatant, a neutralization supernatant and a new solution, and the analysis results are shown in table 11; taking the solution as a research object to develop experimental research;
a. Target addition point: the addition effect of the first-stage supernatant, the first-stage neutralization supernatant and the new liquid is verified through experiments;
b. Experimental conditions: the temperature (85 ℃ C. Of the first-stage supernatant, 80 ℃ C. Of the first-stage neutral supernatant and 40 ℃ C. Of the new liquid) is 60min, and the adding amount of barium carbonate is 1g/L;
c. The results of the experiment are shown in Table 12.
Table 11 2020 shows results of lignin analysis of solutions of various stages from 13 days to 21 days of 4 months
Table 12 Experimental results of delignification addition Point
From table 12, it can be seen that:
the barium carbonate has higher lignin removal rate in a supernatant, a neutralization supernatant and a new liquid, and the technology proves that the technology is feasible for removing lignin sulfonate in zinc sulfate solutions of each stage;
④ Optimal reaction time selection of barium carbonate
A. Solution selection: a first supernatant, a first neutralized supernatant, a new liquid;
b. Experimental conditions: the temperature (85 ℃ C. Of the first-stage supernatant, 80 ℃ C. Of the first-stage neutral supernatant and 40 ℃ C. Of the new liquid) is 30min, 40min, 50min, 60min, 70min, 80min and 90min, and the adding amount of barium carbonate is 1g/L;
c. The experimental results are shown in table 13 and fig. 5;
TABLE 13 Lignin removal reaction time experiment results
As can be seen from table 13 and fig. 5:
The lignin removal rate of the first-stage supernatant, the first-stage neutralization supernatant and the new liquid is gradually increased along with the prolongation of the reaction time, and the lignin removal rate (more than 99.9 percent) is stable after reaching 60 minutes;
according to the judgment, the optimal reaction time of the barium carbonate in a section of supernatant, a neutralization supernatant and a new liquid is only required to be more than 60 minutes, and the reaction time is adjusted according to different solution operation environments;
⑤ Selection of the optimum addition amount of barium carbonate
A. Solution selection: a first supernatant, a first neutralized supernatant, a new liquid;
b. Experimental conditions: the temperature (85 ℃ C. Of the first-stage supernatant, 80 ℃ C. Of the first-stage neutralized supernatant and 40 ℃ C. Of the new liquid) is 60 minutes, and the adding amount of the barium carbonate is 0.2g/L, 0.5g/L, 0.8g/L, 1.0g/L, 1.2g/L and 1.5g/L;
c. the experimental results are shown in table 14 and fig. 6;
TABLE 14 delignification of experimental results
As can be seen from table 14 and fig. 6:
1) A supernatant of: the lignin removal rate gradually rises along with the increase of the addition amount, and the lignin removal rate (more than 99.9 percent) is stable after the addition amount reaches 0.5 g/L;
2) Neutralizing the supernatant: the lignin removal rate gradually rises along with the increase of the addition amount, and the lignin removal rate (more than 99.9 percent) is stable after the addition amount reaches 1.0 g/L;
3) New liquid: the lignin removal rate gradually rises along with the increase of the addition amount, and the lignin removal rate (more than 99.9 percent) is stable after the addition amount reaches 0.5 g/L;
⑥ Knot (S)
A. optimal addition point of barium carbonate: a first supernatant, a first neutralized supernatant, a new liquid;
b. The reaction time of barium carbonate in the solution is more than 60 min;
c. the best adding amount of barium carbonate: 0.5g/L in the first supernatant, 1.0g/L in the first neutralization supernatant, and 0.5g/L in the new liquid.
(5) Study of reducing sugar removal technique
① Hydrogen peroxide removal
The general lignin sulfonate contains 0.5-40% of reducing sugar (the low-sugar lignin sulfonate is selected from outsourcing in production, the content of the reducing sugar is controlled to be within 6%), and hydroxyl free radicals are generated by the combined action of hydrogen peroxide and ferrous iron and act on the reducing sugar to decompose the reducing sugar;
a. solution selection: pre-neutralizing supernatant, a neutralizing supernatant;
b. Experimental conditions: the temperature is 80-85 ℃, the time is 60min for pre-neutralizing the supernatant and 70min for neutralizing the supernatant, and the hydrogen peroxide is added (3.5 g/L for pre-neutralizing the supernatant and 4.5g/L for neutralizing the supernatant);
c. The experimental results are shown in Table 15;
TABLE 15 Hydrogen peroxide addition removal of reducing sugar Experimental results
From the experimental results in table 15, it can be seen that:
under the optimal condition of removing TOC by hydrogen peroxide, the removal rate of reducing sugar in the pre-neutralization supernatant and the first-neutralization supernatant is 100 percent. Therefore, the removal of the reducing sugar can be synchronously completed under the same condition in the TOC removal process of the hydrogen peroxide.
② Copper hydroxide removal
The general lignin sulfonate contains 0.5-40% of reducing sugar (the low-sugar lignin sulfonate is selected from outsourcing in production, the content of the reducing sugar is controlled to be within 6%), copper sulfate is used for dissolving under alkaline conditions to produce copper hydroxide, the copper hydroxide reacts with the reducing sugar under the condition of pH of 5.0-5.4, the reducing sugar is removed, meanwhile, brick-red cuprous oxide precipitation is produced, and finally, the removal of reducing matters in zinc sulfate solution in the hydrometallurgical process is realized. And adding zinc copper salt solid or aqueous solution into sodium hydroxide and lignin sulfonate solution to remove reducing sugar in lignin.
The reaction equation of reducing sugar (mainly glucose) and copper hydroxide under alkaline condition is as follows:
C6H12O6+8CuSO4＝4Cu2O↓+6H2O+8SO2↑+6CO2
Firstly, source elimination: before lignin preparation, mixing copper sulfate with sodium hydroxide solution, preparing fresh copper hydroxide, adding the fresh copper hydroxide into lignin solution in a lignin preparation tank, heating dispersant solution to 65-95 ℃, stirring for 20-60 min, controlling pH to 5.0-5.4, and using the completely reacted solution as a qualified dispersant for oxygen-delivering pressure leaching process.
And secondly, process reduction: copper sulfate is mixed with sodium hydroxide solution, ore pulp containing copper hydroxide is added into a first-stage purifying operation tank, reducing sugar in the solution is removed, and all sediment is deposited into slag.
However, from the laboratory and production, it is found that the copper hydroxide suspension slurry must be prepared newly, i.e. used immediately after preparation, otherwise blackening easily affects the reducing sugar removal effect.
(6) Activated carbon experiments
The method for removing organic matters in the solution by utilizing the physical adsorption, chemical adsorption and other performances of the activated carbon.
A. influence of activated carbon on TOC removal efficiency of ozone and hydrogen peroxide in pre-neutralization supernatant
1) Experimental solution: pre-neutralizing the supernatant;
2) Experimental temperature: 80 ℃;
3) Reaction time: 100min (hydrogen peroxide is added when reacting to 40 min);
4) Experimental agent: ozone, hydrogen peroxide (hydrogen peroxide content 30%), activated carbon;
5) The results of the experiment are shown in Table 16.
TABLE 16 influence of activated carbon on TOC removal efficiency of ozone and Hydrogen peroxide in Pre-neutralized supernatant
From table 16, it can be seen that:
The activated carbon is added in the process of removing TOC from the pre-neutralized supernatant by using ozone and hydrogen peroxide, so that higher TOC removal rate can be obtained, the destroyed organic matters are adsorbed on the activated carbon by utilizing the adsorption effect of the activated carbon, and the activated carbon and the adsorbed organic matters are brought out of the system through solid-liquid separation of a filter press, so that the TOC content in the zinc sulfate solution is reduced.
B. Influence of activated carbon on TOC removal efficiency of ozone and hydrogen peroxide in a neutralization supernatant
1) Experimental solution: a neutralization supernatant;
2) Experimental temperature: 80 ℃;
3) Reaction time: 90min (hydrogen peroxide is added when reacting to 20 min);
4) Experimental agent: ozone, hydrogen peroxide (hydrogen peroxide content 30%), activated carbon;
5) The experimental results are shown in Table 17.
TABLE 17 influence of activated carbon on TOC removal efficiency of ozone and Hydrogen peroxide in a neutralized supernatant
From table 17, it can be seen that:
adding active carbon in the process of removing TOC from the neutralized supernatant by using ozone and hydrogen peroxide, obtaining higher TOC removal rate, adsorbing destroyed organic matters on the active carbon by using the adsorption effect of the active carbon, carrying the active carbon and the adsorbed organic matters out of the system by solid-liquid separation of a filter press, and reducing the TOC content in the zinc sulfate solution.
(7) Radio frequency activation experiments
And carrying out radio frequency activation treatment on the solution in the reaction cavity by utilizing radio frequency activation equipment through microwave activation.
A. Experimental equipment
1) Radio frequency activation system: generating a radio frequency of 750Hz;
2) An ozone generator: ozone concentration of 0-300 mg/L and flow rate of 0-5L/min (QLO-10G) is generated;
3) The reactor comprises: volume 0.94m 3;
4) And (3) a circulation tank: volume 0.78m 3.
B. experimental materials
1) Precursor solution: neutralizing the supernatant;
2) Additive: ozone and hydrogen peroxide.
C. Experimental analysis results
1) First group of
Ozone addition: 300mg/L,5.5L/min; hydrogen peroxide addition amount and frequency: 50mL/30min; sampling interval: 20 min/time; the reaction time was 3 hours in total.
The results of the experiment are shown in Table 18 and FIG. 7.
Table 18 radio frequency experiment first set of analytical data
2) Second group of
Ozone addition: 300mg/L,5.5L/min; hydrogen peroxide addition amount and frequency: 50mL/10min; sampling interval: 30 min/time; the reaction time is 3 hours in total;
The experimental results are shown in table 19 and fig. 8;
table 19 radio frequency experiment second set of analytical data
3) Third group of
Ozone addition: 300mg/L,5.5L/min; hydrogen peroxide addition amount and frequency: 100mL/10min; sampling interval: 1 h/time; the total reaction time is 4 hours;
The results of the experiment are shown in Table 20 and FIG. 9.
Table 20 radio frequency experiment third set of analytical data
According to the analysis results of the three groups of radio frequency activation experiments, the TOC removal rate in the second neutralization supernatant fluid gradually rises along with the increase of the reaction time and the increase of the hydrogen peroxide consumption.
The various embodiments are described in a progressive manner, each embodiment focusing on differences from the other embodiments, and identical and similar parts between the various embodiments are sufficient to be seen with each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. A method for deeply removing TOC and residual organic matters in zinc sulfate solution is characterized by being applied to a zinc hydrometallurgy neutralization iron removal section, and comprises the following steps: copper deposition operation, pre-neutralization operation, first neutralization operation, second neutralization operation and first purification operation, wherein the applied solution comprises the following components: copper precipitation post-liquid, pre-neutralization supernatant, first neutralization supernatant, second neutralization supernatant, middle supernatant solution, first section purified post-liquid and new liquid;
The method adopts an ozone aeration method and a strong oxidation method;
Wherein the strong oxidation method and the ozone aeration method are performed in a reaction tank for pre-neutralizing supernatant and/or a neutralizing supernatant, the strong oxidation method is performed in a reaction head tank, and the ozone aeration method is performed in a reaction tail tank;
the oxidant adopted in the strong oxidation method is H 2O2, and the H 2O2 is sprayed into zinc sulfate solution by pressurized oxygen-enriched air;
and adding barium carbonate into the zinc sulfate solution, wherein the adding point of the barium carbonate is any one of a supernatant, a neutralization supernatant and a new liquid.
2. The method for deep removal of TOC and residual organics from zinc sulfate solution according to claim 1, further comprising adding activated carbon to the pre-neutralization supernatant and/or a neutralization supernatant.
3. The method for deeply removing TOC and residual organics from a zinc sulfate solution according to claim 1 further comprising radio frequency activation of the second neutralization supernatant.
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